JPH03140309A - Multimetal catalyst, preparation thereof, and polymer prepared therewith - Google Patents

Abstract

Disclosed is a polymetallic supported catalyst component comprising an activated anhydrous MgCl2 solid support which has been treated with at least one treatment of at least two halogen-containing transition metal compounds, wherein one is a halogen-containing titanium metal compound and one is a halogen-containing non-titanium transition metal compound, optionally, in the presence of an electron donor and the processes for producing the component. A catalyst for the polymerization of at least one alpha-olefin of the formula CH2=CHR, where R is H or a C1-12 branched or straight chain alkyl or substituted or unsubstituted cycloalkyl, by reacting this supported catalyst component with an organometallic cocatalyst, optionally in the presence of an electron donor, and the polymerization of at least one alpha-olefin with the catalyst are also disclosed. The resulting Polymers, particularly propylene polymers, have a controllable atactic content, which is expressed herein in terms of its xylene solubility at room temperature (XSRT), wherein the ratio of the I.V. of the XSRT fraction to the I.V. of the bulk polymer is greater than or equal to 0.50.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multimetal supported catalyst component, a method for preparing a multimetal supported catalyst component, a Ziegler-Natsuta catalyst prepared from the component, a formula CM, =CHR (wherein R is H or C1~
1□ A method for polymerizing at least one α-olefin (branched or straight-chain alkyl or unsubstituted or substituted cycloalkyl), and olefin polymers produced using the catalyst.

The polymerization of α-olefins, especially propylene, with Ziegler-Natsuta catalysts involving reaction products of organometallic compounds and transition metal compounds to produce highly crystalline isotactic polymers is known. Typically, the highly crystalline intact fraction was separated from the amorphous and low molecular weight and semi-crystalline fractions by extraction with a hydrocarbon solvent such as hexane or kerosene. Research activity in this area since the advent of these catalysts has generally been related to improvements in yield, stereospecificity, and morphology of crystalline intact polymers. It is a highly active and highly stereospecific compound containing TiCl 4 and an electron donor compound (Lewis base) supported on an active anhydrous MgCj22 solid catalyst component and an organoaluminum activator as a cocatalyst with or without the electron donor. This was achieved through the development of a catalyst system. Propylene homopolymers typically produced with two catalysts are “CN
Isotacticity greater than 95% and 2-5 as determined by MR analysis and number fraction of isotactic pentads.
%XSRT of r, v of the XSRT fraction and 1. The ratio with V, is less than 0.50. Despite the suitability of this catalyst system, it does not provide a certain light weight with elastic properties, nor does it allow the production of high molecular weight, active polymers.

U.S. Patent No. 4.562.170; 2a and 3 of the periodic table
Supported catalyst components for the polymerization of alpha-olefins, especially ethylene, requiring gold, oxide support materials from metals of the AS4a and 4b groups are described. Supported component:′! Form a slurry of gold oxide, preferably dehydrated high surface area gold oxide, add a solution of organomagneside metal, add a solution of hafnium compound and react, add a halogenating agent and react, and prepare tetravalent titanium. It is prepared under anhydrous conditions by successive steps of adding and reacting compounds and recovering solid catalyst components. It is used with organoaluminum cocatalysts in the polymerization of ethylene. Similar catalyst systems are disclosed in U.S. Pat. Nos. 4,554,265 and 4,61, except that the organomagnesium compound in solution is first reacted with a zirconium compound in solution rather than with a hafnium compound.
8.660.

U.S. Patent Nos. 4.578.373 and 4□665.
No. 262 is based on the aforementioned U.S. Pat. No. 4,562.170, No. 4
, 554.265 and 4,618,660. The main difference appears to be that a solution of a zirconium compound, a hafnium compound or a mixture thereof is used instead of a solution of a hafnium compound or a solution of a zirconium compound.

U.S. Patent Nos. 4,310,648 and 4,356.
No. 111 discloses an olefin polymerization catalyst component prepared by reacting a trivalent or tetravalent titanium compound, a zirconium compound, and a halogen source such as ethylaluminum dichloride. .

In one embodiment, the present invention provides at least I treatment of at least two halogen-containing transition metal compounds, one being a halogen-containing titanium metal compound and one being a halogen-containing non-titanium transition metal compound, optionally with an electron donor. An aspect of the present invention is to provide a polymetal-supported catalyst component containing a treated activated anhydrous Mg12 or its alcohol adduct solid support in the presence of active anhydrous % (gCβ2, its alcohol adduct or treating the precursor with at least two sequential or even simultaneous treatments of at least two halogen-containing transition metal compounds, one being a halogen-containing titanium compound and one being a halogen-containing non-titanium transition metal compound;
optionally in the presence of a polar, substantially inert solvent in which the metal compound is at least slightly soluble and in which the support is substantially inert, and optionally in the presence of an electron donor. preparing a multimetal-supported catalyst component comprising treating the catalyst at a temperature of 0''C and then at a temperature of about 30 to about 120'C for 30 to 240 minutes for each treatment, with the solids separated in the middle of the treatment. This is the way to do it.

In other embodiments of the invention, 2CH2=CHR, where
R is H or C8-1□ technical or direct alkyl or substituted or unsubstituted cycloalkyl). , optionally in the presence of an electron donor. When substituted, cycloalkyl is preferably substituted in the 4-position. Typically the substituents are 61-1□alkyl or halide or both.

Another aspect of the invention is that at least one α having the formula
- Four combinations of olefins with the catalyst of the present invention.

In still other embodiments, the present invention provides controllable acid content expressed in terms of xylene solubility at room temperature (XSRT), wherein the xylene soluble fraction I, V, and bulk polymer 1. Provided are polymers, in particular propylene polymers, exhibiting a ratio of V.

Active sluice gCj2z carrier is disclosed in U.S. Pat. No. 4,544,7
No. 17, No. 4,294.721 and No. 4.220.
No. 554, herein incorporated by reference.

Alternatively, the solid catalyst support forms an adduct of magnesium dichloride with an alcohol, such as ethanol, propatool, butanol, isobuknol and 2-ethylhexanol, in a molar ratio of 1:1 to 1:3, and then It can be prepared by further processing according to the invention.

In another method, a magnesium dichloride/alcohol adduct containing equimolar moles of alcohol per mole of MgCffi□ in -S is prepared by mixing the alcohol and magnesium chloride in an inert hydrocarbon liquid that is immiscible with the adduct. , heating the mixture to the melting temperature of the adduct and at the same time e.g.
Tara, Kusu (UltraTurrax) T-45N
SII'JJ can be achieved by stirring vigorously at 20°C to 5000rpm using a stirrer.The resulting emulsion is quickly cooled and the adduct is processed into spherical particles until it becomes hard. The particles are prepared under an inert atmosphere, such as nitrogen, at a temperature of 50°C to 1.30°C and an alcohol content of 1.30°C.

It is dried and partially dealcoholized by increasing the temperature for a sufficient period of time to reduce from 3 moles per mole to 1 to 1.5 moles per mole. The resulting partial dealcoholization adduct is 50~
Average diameter of 350 microns, So
B using rptomatic) 1800 equipment,
Surface area of approximately 9-50 bo/g by E, T, and 0.6-2 cc/g as measured by mercury porosimeter
It is in the form of spherical particles with a porosity of . For example, Mg
The Ce3.3ROH adduct (wherein R is straight chain or branched C2-1o alkyl) can be prepared by stirring for 10
4.399.054, except that it was carried out at 3,000 rpm instead of .
referenced. The adduct particles formed were collected by filtration, washed three times with 500 d aliquots of anhydrous hexane at room temperature, and washed with MgCl! under nitrogen. , by increasing the temperature from 50°C to 130°C for a sufficient time to reduce the alcohol content from 3 to about 1.5 moles per mole.

Activated MgCl2 can be activated prior to treatment with a halogen-containing transition metal compound, or can be formed in situ from a precursor of MgClz under conditions that form and activate magnesium dichloride. One such condition is the reaction of a halogen-containing titanium compound, such as titanium tetrachloride, with a Mg compound, such as Mg(OEt)t, at 30 DEG to 120 DEG C. under stirring, -C, at about 250 rpm. The important point is the use of active MgCfz, not the method of obtaining it.

The solid catalyst supporting component is anhydrous active MgC/! ．． , its alcohol adduct or its non-activated precursor in an inert atmosphere, a succession of at least two halogen-containing transition metal compounds, one being a halogen-containing titanium compound and one being a halogen-containing non-titanium transition metal compound. or simultaneously or both, initially at 0°C and then at 30-12°C, optionally in the presence of a polar liquid medium.
It is formed by processing at a temperature of 0° C. for 30 to 240 minutes, with the solid separated in the middle of the process. The order of treatment with halogen-containing transition metal compounds and their relative amounts are used to influence catalyst activity and polymer properties. Preferably, the support is first treated with a halogen-containing titanium compound or a combination of a halogen-containing titanium compound and at least one halogen-containing non-titanium transition metal compound.

It is preferred to use a combination of two compounds in the first treatment in order to obtain a predominantly active polymer, ie one with a highly xylene soluble fraction. A preferred combination is a halogen-containing titanium compound and a halogen-containing zirconium compound or a halogen-containing hafnium compound. In order to obtain a predominantly isotactic polymer, ie one with a low xylene solubility fraction, it is preferred to first treat the support with a halogen-containing titanium compound in the presence of an electron donor.

After the initial treatment, the solids are separated and treated again with various combinations of halogen-containing transition metal compounds one or more times, with the solids separated between treatments.

The halogen-containing transition metal compound is at least slightly soluble and the solid activated anhydrous MgCj! Any polar liquid medium in which the z-support is substantially insoluble and substantially inert with respect to the various components of the supported catalyst component, but with which it is capable of interacting, may be used.

When prepared from anhydrous activated MgCl2 or its unactivated precursor, such activated solid catalyst components exhibit a high concentration in the spectrum of unactivated magnesium dichloride (having a surface area of less than 3 I/g). Either there is no strongest diffraction line that appears and in its place a broadened halo appears shifted with respect to the position of the strongest line in the deactivated spectrum and appears at its maximum intensity, or the strongest diffraction line appears in the X-ray spectrum of deactivated magnesium dichloride. It exhibits an X-ray spectrum with a half-peak width at least 30% larger than that of the strongest diffraction line feature.

MgCffi□ ・3R dealcoholized as above
When prepared from the OH adduct, the solid catalyst component prepared therefrom exhibits a magnesium chloride reflection exhibiting a halo with maximum intensity between 33.5° and 35″ 2θ angles, and 14
．． It has a 95° 2θ reflection-free X-ray spectrum.

The symbol 2θ=Bragg angle. Suitable halogen-containing transition metal compounds useful in preparing the multimetallic catalyst support components of the present invention include Sc, Ti, Zr, tlf, V, Nb and T.
Includes halides, oxyhalides, alkoxyhalides, l:: )' IJ dohalides and alkyl halides of a.

Halogen can be chlorine or bromine.

Alkoxy and alkyl halides typically have 1 to 12 carbon atoms and are both straight chain and branched. Chlorides of Ti, Zr and Hf are preferred.

Scandium trichloride and scandium tribromide are typical scandium compounds useful in preparing the support components of the present invention. Scandium trichloride is preferred.

Examples of suitable titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium oxychloride, titanium bromide, and trichlorotitanium ethoxide.

Titanium tetrachloride is preferred, and one suitable zirconium compound:
Bad breath (includes hyzirconium, zirconyl bromide and zirconyl chloride; zirconium tetrachloride is highly preferred).

Typical hafnium compounds include hafnium tetrachloride, hafnium tetrabromide, hafnium oxy/bromide, and hafnium oxychloride. A preferred hafnium compound is hafnium tetrachloride.

Suitable vanadium compounds include vanadium tetrachloride, vanadium tetrabromide, vanadyl chloride and vananyl bromide. Vanadyl chloride is preferred.

Suitable 22obium compounds include niobium pentachloride, niobium pentabromide, niobium oxychloride and niobium oxychloride. Preferred niobium compound: niobium pentachloride.

Typical tantalum compounds useful in the practice of this invention include bicyclic (hytantalum and tantalum pentabromide).
Hittantal is preferred).

The amount of transition metal compound used in the preparation of the solid-supported catalyst component of the present invention ranges from 5 to 1,00 mol, preferably from 10 to 50 mol, most preferably from 10 to 1,00 mol per mole of MgCff1z.
It is 25 moles. The ratio of Ti metal to other transition metals or transition metals is typically between 10:1 and 4, as the case may be.
000:1, preferably 250:1 to 25:1.

The transition metal compound can be used neat or in a substantially inert polar liquid medium.

Preactivated anhydrous MgCl2 or Mg compounds capable of forming activated MgClz when treated with halogen-containing titanium metal compounds at temperatures between 30 and 120<0>C can be used.

Typically, the reaction components in a 1 liter container are about 250 to
Stir at 300 rpm. The reaction generally takes about 30 to about 240 minutes, preferably 60 to 180 minutes for each treatment.
minutes, most preferably 80 to 100 minutes. Typical polar media useful in preparing supported catalyst components include acetonitrile, methylene chloride, chlorobenzene,
(1), 2-dichloroethane and a mixture of chloroform and a hydrocarbon solvent are included. methylene chloride and 1,2
Dichloroethane is a preferred polar liquid medium.

When a mixture of chloroform and a hydrocarbon material is used, suitable hydrocarbon materials include kerosene, n-bentane,
isopentane, n-hexane, isohexane and n-
Contains hebutane. n-hexane is a preferred hydrocarbon material.

Suitable electron donors for use in preparing the supported catalyst components of the invention include acid amides, acid anhydrides, ketones, aldehydes and monofunctional and difunctional organic acid esters having from 2 to 15 carbon atoms, such as acetic acid. Methyl, ethyl acetate, vinyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl benzoate, ethyl benzoate, butyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, amyl toluate, Includes methyl anisate, ethyl ethoxybenzoate, ethyl bivalate, ethyl naphthoate, dimethyl phthalate, dimethyl phthalate and diisobutyl phthalate (DIBP). Furthermore, 1, 3- and 1. can be substituted on all carbons, preferably having substitution on at least one of the internal carbons. - 1- and 1.5- and larger diethers can be used. Suitable diethers include 2,2-diisobutyl-13-dimethoxypropane, 2-isopropyl-
2-isobenthyl-13-dimethoxypropane, 22-
Bis(cyclohexylmethyl)-1,3-dimethoxypropane, 23-diphenyl-1,4-jethoxybutane, 2,3-dicyclohexyl-1,4-jethoxybutane, 2,3-dicyclohexyl-1,4-dimethoxy Butane, 2,3-bis(p-fluorophenyl)-1,4
-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxybencune and 2,4-diitubrovir-1,
Includes 5-dimethoxybencune. Difunctional esters such as diisobutyl phthalate are preferred.

The supported catalyst component prepared according to the invention is recovered and washed with a number, e.g., 5 to 20, aliquots of a substantially inert solvent. Suitable solvents for washing the catalyst components include: methylene chloride, 1,2-dichloroethane, hexane, and chloroform/hexane mixtures in which the amount of chloroform is between 10 and 75% of the mixture.

Catalyst component: in the dry state or as a slurry in a suitable non-reactive cloud, i.e. under an inert atmosphere without exposure to heat or light, either artificial or natural, for at least 6 months. , can be stored for up to several years.

Organometallic compounds suitable for use in preparing the catalysts of the invention include organoaluminum compounds, organogallium compounds,
Includes finite transition metal compounds, organomagnesium compounds and organozinc compounds.

- Alkylaluminum compounds are preferred.

Triisobutylaluminum (TIB, A, L), diisobutylaluminum hydride (DIBAL-H), diisobutylaluminum ethoxide, triethylgallium, triethylaluminum (TEAL), triisopropylaluminum, diisobutylzinc, diethylzinc,
Dialkylmagnesiums, such as dimethylmagnesium and diethylmagnesium, and compounds containing two or more Afl atoms bonded to each other through a heteroatom, such as: (C21(S) 2A+-0-AI (C21(S)
2; and (C211s)AI-0-3-0-AI (C2H5)
2 is a typical metal alkyl compound. Generally, from about 5 to about 20 per 0.005 to 0.05 g of supported catalyst component.
Millimoles of organometallic activator are used.

Suitable electron donors for use with organometallic compounds have at least two alkoxy groups attached and -〇COR,
It is an olga/silane compound having silicon (rV) as a central atom to which -NR2 or -R group or two groups thereof which can be the same or different are bonded, and R in the above formula has 1 to 20 carbon atoms. alkyl, alkenyl, aryl, arylalkyl or cycloalkyl with Such compounds are described in U.S. Patent No. 4.472.5.
No. 24, No. 4.522.930, No. 4.560.67
No. 1, No. 4.581°342 and No. 4.657.8
It is described in No. 82.

Furthermore, S+ where the nitrogen is part of a 5- to 8-membered heterocyclic ring
Organosilane compounds containing N bonds can be used. Examples of such organosilane compounds are diphenyldimethoxysilane (DPMS), dimesityldimethoxysilane (DMMS), t-butyl (4-methyl)
These are piperidyldimethoxysilane (TB4MS), t-butyl (2-methyl) piperidyl dimethoxysilane, isobutyl (4-methyl) piperidyl dimethoxysilane, dicyclohexyldimethoxysilane, t-butyltriethoxysilane and cyclohexyltriethoxysilane. Dimesityldimethoxysilane and t-butyl (
4-Methyl)biveridyldimethomexisilane is preferred. A method of manufacturing TB4MS is disclosed in US Patent Application No. 386.183, filed July 26, 1989, the disclosure of which is hereby incorporated by reference. The remaining silane is commercially available.

The Mg:Me ratio in the catalyst of the present invention is from about 0.9 to about 25.
0, the M':Ti ratio is about 0.1 to 25.0, and the Af:Me ratio is about 20 to about 40,000. M
e is Ti5Sc, Zr, Hf, V, Nb, Ta
or a combination thereof. M' is 5cSZrSHf
, V, Nbx Ta or a combination thereof.

α-olefins that can be polymerized by the catalyst of the present invention include ethylene, propylene, 1-butene, ■-pentene, 4-methyl-1-pentene, l-hexene, 1-octene, vinylcyclohexane, allylbenzene, allylcyclohexane, vinyl Cyclobencune or a mixture thereof.

Polymerization reactions using the catalysts of the invention are carried out in an inert atmosphere in the presence of liquid or gaseous monomers or combinations thereof.
in liquid phase polymerization at a temperature of from about 30 to about 100°C, preferably from 50 to 80°C, optionally in the presence of an inert hydrocarbon solvent, from about atmospheric pressure to about 1000 psi, preferably 2
00 to 500 psi, atmospheric pressure to about 60 in gas phase polymerization
Performed at 0 psi pressure. Typical residence time is approximately 1
5 minutes to about 6 hours, preferably 1 to 4 hours.

The catalyst system, i.e., the polymetallic support component, the organometallic activator, and the electron donor when used, is added to the polymerization reactor, whether or not the monomer is already in the reactor, by separate means. The supported catalyst components and activator can be preheated at room temperature for 3 to about 10 minutes prior to polymerization. Mixing is preferred.

The olefin monomer can be added before, during or after addition of the catalyst system to the polymerization reactor. Preferably it is added after addition of the catalyst system.

Hydrogen can be added as a chain transfer agent to reduce the molecular weight of the polymer, if necessary.

The polymerization reaction can be carried out in slurry, liquid or gas phase processes, or in a combination of liquid and gas phase processes using separate reactors, all of which can be carried out batchwise or continuously.

Precontact the catalyst with a small amount of olefin monomer (prepolymerization) by keeping the catalyst suspended in a hydrocarbon solvent.
polymerization at a temperature of 60 DEG C. or lower for a sufficient period of time to yield an amount of polymer from 0.5 to 3 times the weight of the catalyst.

This prepolymerization can also be carried out in liquid or gaseous monomers, in which case amounts of polymer up to 1000 times the weight of the catalyst can be produced.

Unless otherwise indicated, the following analytical methods were used to characterize the supported catalyst component and polymer samples.

The concentration of active metals in the supported catalyst components was determined by atomic absorption spectrometry using a Perkin Elmer Model 3030. For the analysis of Mg, Tf, Sc and
Hydrolyzed with 25 m2 of N-Hf So solution.

Samples were filtered and aliquots diluted as necessary based on metal concentration. The resulting aliquot was analyzed using an analytical method for single atomic absorption spectrometry (Analyt+cal Metho
dsfor Atomic Absorption S
pectrophotometry) =, Parkin
Perkin-Elmer Corp.

Frame AA was analyzed using the standard 1 technique described in NorNalk, CT, ). Similar operation
r and Hf, but 0.2 wt% A
1% HF containing β (added as A C2, 6H20)
A 2N solution was used instead of a 23(14) solution.

Organic compounds in the supported catalyst components were measured by gas chromatography. Sample (0.5-1.0g) in 20ml
Dissolved in acetone, 0.058-0.0 in acetone
10 ml of an internal standard solution of 60 molar n-dodecane was added. When the supported catalyst component contains an electron donor, phthalate di(n-
Butyl) as an internal standard solution to form a 0.035-0.037 mol phthalate di(n-butyl) solution! ;1 added. Then 15% NH4OH was added to the solution at pH 7 to precipitate the metal, which was removed by filtration. The filtrate was analyzed by gas chromatography using an HP-5830 gas chromatograph with FID (flame ionization detector). The column was a 0,530 mm ID fused silica wide-diameter capillary column coated with Supelcowax I be.

The solidity and viscosity of the resulting polymer are as follows: (J, HE
11+ott) et al., Journal of Applied Polymer Science f-7s (J, Appl+ed Po
lymerSci. ), 14.2947-2963
(1970) using an Usoberohde viscometer tube at 135° C. in decalin.

The % xylene soluble fraction was determined by dissolving a 2 g sample in 200 ml quintylene at 135° C., cooling to 22° C. in a constant temperature 1, and immediately filtering through filter paper. An aliquot of the filtrate was evaporated to dryness, the residue was weighed, and the weight percent soluble fraction was calculated.

Melting point and heat of fusion:′! Measurements were made by differential scanning calorimetry (DSC) on a DuPOnt 910 DSC cell using a DuPont 99Q controller. Melting data were obtained at a heating rate of 20°/min after quenching the melt under nitrogen atmosphere.

A Nicolet 360 spectrometer was used as described in J. C. Randall's ``Polymer Sequence Determination''.
(mination) J Academic Press (Aca
demic Press, N, Y, ) (1977
) was used to determine the actic, syndiotactic and isotactic content based on the I3CNMR pentad sequence analysis (of the methyl resonance) described in .

Tensile strength was measured according to ASTM D412 procedures.

Nicolet 740 S X F
A T-infrared spectrophotometer was used to quantify monomer in the copolymer samples.

The following examples are illustrative of specific embodiments of the invention.

In the examples, dry, oxygen-free solvents were used. Solvents were dried by storage on activated molecular sheets or by distillation from CaH. Transition metal compounds were frequently used as received from the manufacturer. The electron donor was dried over activated 4A molecular sieves either neat or as a solution in hexane before use. All preparations of solid-supported catalyst components and polymerization reactions were carried out under an inert atmosphere.

All percentages are by weight unless otherwise indicated. The ambient or room temperature is approximately 25°C.

Example 1 This example illustrates a supported catalyst component and its preparation.

50 m into a reaction vessel equipped with a condenser, adapter and paddle agitator and sparged with nitrogen for approximately 15-20 minutes.
2.5 g (11 mmol) lrc 14 slurried in 1 neat Tack 4 (0.45 mol) was added. The slurry was then cooled to 0° C. in a dry ice/isopar bath while stirring at 1100 rpm. 12.5 % ), 1 g and 50 % ethanol preactivated anhydrous! , 1 g C20 support (5,1
g) was added to the reaction vessel in an inert cloud.

After the carrier addition was complete, the stirring rate was increased to 25 Q rpm, the dry ice/isopar bath was replaced with an oil bath, and the reaction temperature was raised to 110° C. for 1 hour under a low nitrogen flow.

The reaction mixture was maintained under these conditions for 90 minutes. At the end of this period, stirring was stopped and the solids were allowed to settle at 100° C. for approximately 20 minutes. The supernatant was removed and the solid was dissolved in methylene chloride (50rnI!). The sample was washed 5 times at 30°C. Then add 50 ml of TiCl to the solid.

(0.45 mol) was added while stirring at 25 Orpm. The reaction mixture was then stirred with equal amounts and heated to 100° C. for 1 hour under a low flow of nitrogen. Reaction conditions were maintained for 90 minutes. Next 5) Big: The tank was stopped and the solid was allowed to settle at 100°C for about 20 minutes. The supernatant was removed. The solid was washed with 50 parts of hexane three times at 61]C and then three times at room temperature.

The supported catalyst components, slurried in the Saihira washing liquid pile, were transferred into a Schlenk flask. Decant the final wash and transfer the catalyst to approximately 25 inches of vacuum maintained by flushing nitrogen into a vacuum manifold at 50°C.
The catalyst components were shaken periodically and dried until a free flow condition was obtained.
．． It had 3% Ti and 20.2% 2r.

Example 2 The procedure and ingredients of Example I were used, but 3.4 g
(11 mmol) HfCL was used in place of ZrC1a. Catalyst component is 10.7%Kg, 2.3% by elemental analysis
It had Ti and 25.2% Hf.

Example 3 The procedure and ingredients of Example 1 were used, but 1.6 g
(11 mmol) ScC13 was used in place of ZrCl4. The catalyst components are 11.2% Mg and 6.5% T according to elemental analysis.
i and 7.8% Sc.

Example 4 The procedure and ingredients of Example I were used, but 1.7 g
(5.3 mmol) HfCj! n and 1.2g (
5.2 mmol) ZrCff1. 2.5g (11
mmol) was used in place of ZrC1a. The catalyst components are 10.4% Mg, 2.5% Ti, 9.3% Zr by elemental analysis.
and 15.4% Hf.

Example 5 Henito T in a reactor equipped with a condenser, adapter and paddle agitator and sparged with nitrogen for about 15-20 minutes
iC1a (150ml 1.4 mol) was added. TiCQm was then dissolved in a dry ice/isopar bath at 1
Stir at 0.00 rpm and cool to o'c.

Preactivated anhydrous MgCj containing 11.3% 11g and about 55% ethanol! Z support (15.0 g) was added to the reaction vessel under an inert atmosphere. After the carrier addition was completed, the stirring speed was increased to 250 rpm, the dry ice/Isopar bath was replaced with an oil bath, and the reaction temperature was decreased to 1.
The temperature was increased to 100° C. for hours. Diisobutyl phthalate (DIBP) (3
, 6, 14 mmol) was added dropwise using a syringe. The reaction mixture was maintained at 100°C for 90 minutes. At the end of this period, stirring was stopped and the solids were allowed to settle at 100'C for approximately 20 minutes. Remove the supernatant liquid and add 1°2 to the resulting solid.
- to ZrC in dichloroethane (300 precepts).

A slurry of (3.0 g, 13 mmol) was charged.

The reaction mixture was then heated to 60°C for 30 minutes while stirring at 250 rpm under a low flow of nitrogen. Reaction conditions were maintained for 90 minutes. At the end of this period, stirring was again stopped and the solids were allowed to settle at 60° C. for approximately 20 minutes. The supernatant liquid was removed and the solid was dissolved in 10oC of 1,2-dichloroethane.
It was washed 5 times at 60° C. and 3 times at room temperature in the Id section. The supported catalyst component was then washed twice with 100 d parts of hexane at room temperature. The supported catalyst components were transferred into a Shusink flask during slurry in the final wash. Decant the last wash and
The catalyst was dried under 25 inches of vacuum at 50° C. with periodic shaking until a free-flowing powder was obtained. The catalyst components are 15.6% Mg, 1.3% Ti, 6% by elemental analysis.
．． It had 4% Zr and 6.9% DIBP.

Example 6 The procedure and ingredients of Example 5 were used, but methylene chloride was used instead of 1,2-dichloroethane and 40<0>C was used instead of 60<0>C. The catalyst component was 16.4 by elemental analysis.
%Mg, 1.9%Ti, 4.6%Zr and 5.9%D
I had IBP.

Example 7 The procedures and components of Example 5 were used, but preactivated anhydrous MgCe was used instead of 14.8 g of support for 15.0 g, and 7,2d (27 mmol) DIBP was replaced with 3.6 dDIRP. used instead of. The catalyst components had 15.8% Mg, 2.5% Ti, 2.4% Zr and 8.3% DIBP by elemental analysis.

Example 8 This example illustrates another supported catalyst component of the present invention and its method of preparation.

5. Into a container sparged with argon for approximately 15-20 minutes.
2 g (22 mmol) ZrC1 was added.

50d (0.45 mol) neat TiC 1 m was then added and shaken or swirled intermittently until a slurry was formed (approximately 5-20 minutes). The resulting mixture was heated to 2-5 psi.
under a low argon flow into a reaction vessel equipped with a septum cap and stirring paddle that was sparged with argon for 15-20 minutes before transfer. The slurry was then cooled to O'C in a dry ice/isovar bath while stirring at 200 rpm. Preactivated anhydrous Mt containing 11.3% Mg and approximately 55% ethanol; Cffi□ support (
5.6 g) was added to the reaction vessel under an inert atmosphere. After the carrier addition was complete, the septum Kimap was replaced with a ground glass stopper and stirred (the baking speed was increased to 300 rpm and the dry ice/Isopar bath was replaced with an oil bath. The Fi reaction mixture was heated to 100° C. for 1 hour; The temperature was then maintained for 3 hours, at the end of which time the stirring was stopped and the solids were
It was allowed to settle for about 20 minutes at 0°C.

The supernatant was removed and 200ml of anhydrous hexane was added.

The mixture was then heated to 60° C. for 10 minutes with a stirring speed of 300 rpm. Then, the stirring was stopped and the solids were
It was allowed to settle for about 5 minutes at 0°C. The supernatant was removed. Add the solid four more times with 200d hexane at 300 rpm.
The solids were washed in the same manner by slowly heating to 60° C. for 10 minutes, stopping stirring, allowing the solids to settle at 60° C. for about 5 minutes, and removing the supernatant liquid. Next, the solid was washed five times in the same manner at room temperature. The resulting supported catalyst component was then suspended in 150 ml of beef starch in 5) and transferred into a pond reaction vessel under a flow of argon. Harden at room temperature for about 30 minutes
After settling for a minute, the hexane was removed. The catalyst components were dried at 50° C. under about 20 inches of vacuum maintained by flowing argon into the vacuum manifold until substantially all free solvent disappeared. The pressure was then reduced to about 25 inches of vacuum and the catalyst components were shaken periodically until a free flowing powder was obtained. The catalyst components are 6.0% Mg, 5.5% Ti, 25.9% Zr and 5% by elemental analysis.
4.1%C! It had

Example 9 The procedure and ingredients of Example 8 were used, but 5.0 g
(22 mmol) of ZrCl and 4.9 g of the pre-activated product, the resulting catalyst component was washed with anhydrous methylene chloride 50 d at 30°C for 10 minutes at 300 rpm (washed with anhydrous methylene chloride 5 times). Elemental analysis revealed that the catalyst components were 6.7% Mg, 6.1% Ti.
, 20.2% Zr and 54.8% C1.

Example 10 The procedure and ingredients of Example 8 were used, but 2.5 g
(11 mmol) ZrCl! , 4 and 5. Ogg
The activated support was used to wash the catalyst components according to the procedure of Example 9. Elemental analysis shows that the catalyst component is 10.1% Mg, 5.
0% Ti, 15.6% Zr and 56,4% C! It was shown that it contains

Example 11 The procedure and ingredients of Example 8 were used, but 1.0 g
(4.3 mmol) ZrC14 was substituted for 5.2 g of preactivated anhydrous MgC12z support.5. Og 5.6
g, reaction conditions were maintained for 90 minutes instead of 3 hours, and 50 d parts of methylene chloride was mixed with 20 (1 d parts) of anhydrous hexane.
Used for cleaning instead of part 1d, changing the cleaning temperature from 30℃ to 60℃
After the final wash at 60° C. in Example 8, but before transferring to another reaction vessel for drying, the following procedures and ingredients were used instead.

1,0 g ZrCl! 4 and 50d-1T:C1
, was added to the solids formed after the final wash and the reaction mixture was heated to 100'C for 1 hour at 30 rpm under argon.The reaction conditions were maintained for 90 minutes.The stirring was then stopped and the solids It was allowed to settle for about 30 minutes at 100° C. The supernatant liquid was then removed and the resulting solid was washed five times at 30° C. with 50 d parts of methylene chloride, then twice at 30° C. with 1 part of 50 Inn of hexane, and 50 ml of hexane. Elemental analysis contained 11.4% Mg, 0.9% Ti and 15.3% Zr.

Example 12 The procedure and ingredients of Example 8 were used, but 2.5 g
(11 mmol) ZrCl! 4.4 was used instead of 5.2 g, and 4.9 g of preactivated anhydrous MgCl2 support was added to 5.2 g.
6 g instead, reaction conditions were maintained for 90 minutes instead of 3 hours, 50 parts of 1,2-dichloroethane were used in the wash instead of 200 parts of anhydrous hexane, and after the final wash at 60°C, but after drying. The following procedures and ingredients were used before transferring to another reaction vessel for the reaction.

The solid was then washed once with 50 d hexane at 60°C as in the other washes. NEET Tic la (50r
d) was added to the solid formed after this last wash and the reaction mixture was heated to 100° C. under argon with stirring at 30 Orpm for 1 hour. Reaction conditions were maintained for 90 minutes. Stirring was then stopped and the solids were allowed to settle at 100"C for about 20 minutes. The supernatant was then removed and the resulting solids were washed three times with 50 parts hexane at 60°C and then three times with 50 parts hexane at room temperature. It was washed in the brewery.Elemental analysis showed that the catalyst component was 1.
It was shown to contain 2.4% Mg, 1.3% Ti and 15.5% Zr.

Example 13 The procedure and components of Example 8 were used, but ZrCf
Anhydrous MgCN preactivated without using a.

Carrier 5. Og was used instead of 5.6 g, reaction conditions were maintained for 90 minutes instead of 3 hours, and then the following procedures and ingredients were used before washing.

A slurry of 1.0 g (4.3 mmol) ZrC14 in 100 ml of 1,2-dichloroethane was added to the resulting solid, and the reaction mixture was stirred under argon for 1 hour at 300 mL.
Heat to 60°C with stirring at rpm. 9 reaction conditions
It was maintained for 0 minutes. Then the stirring was stopped and the solids were
The mixture was allowed to settle for about 20 minutes at °C. Then remove the supernatant,
The resulting solid was heated at 60°C with 50 d parts of 1,2-dichloroethane.
The sample was washed 5 times with water, 3 times at room temperature, and 2 times with 50 ml of helium soil at room temperature. Elemental analysis shows that the catalyst component is 13.0%.
Example I4 The procedure and ingredients of Example 3 were used, but lrC
Pre-activated anhydrous without using R+! ,! 5.1 g of gcp2 carrier was used instead of 5.6 g, reaction conditions were maintained for 3 hours: 90 minutes, and then used for the next steps and ingredients before washing.

1, Og (4,3 mmol) 2rl-, f<
A slurry of 10 (11%) of 1,2-dichloroethane was added to the resulting solid, and the reaction mixture was heated under argon for 300 min.
The reaction conditions were heated to 60° C. for 30 minutes with stirring at rpm and maintained for 60 minutes. The heating was then stopped and the solids were allowed to settle at 60°C for approximately 20 minutes.

Next, remove the supernatant liquid in step 1, and remove the resulting solid using a 1,2-sieve 0
mouth ethane 50. The tube was washed 5 times at 60° C., 3 times at room temperature, and 2 times at room temperature with 50 ml of hexane.

Elemental analysis shows that the catalyst component is 12.6%),)g, 3.2%T
1 and 10.2% Xr.

Example 15 The procedure and ingredients of Example 5 were used, but 12.0
Preactivated M containing % Mg and approximately 50% E tOH
gCe z carrier 5. 11.3%ng and approx.
% ethanol in place of 15.0 g MgCj2□ carrier, TiCff1.50rd (0.45 mol)
was used in place of 150ml and DI before the first solids separation.
BPl, 2d (4,5 mmol) was used instead of 3.6 d, 0.5 g (2,2 mmol) ZrC1a and 0
．． 7 g (2.2 mmol) 1.2 of HfCff4
- the mixture in dichloroethane 100rd; 3. Og
In addition to the resulting solid in place of a slurry of ZrC14 in 300d1,2-dichloroethane, 50 goose wash volumes (1
) was used instead of 00d. Elemental analysis shows that the catalyst component is 15
．． 8%Mg, 1.3%Ti, 3.3%Hf, 4.2%Z
r and 5.4% DIBP.

Example 16 The procedure and ingredients of Example 8 were used, but ZrC1
5. Anhydrous MgCj22 support preactivated without using a.
Using Og instead of 5.6g, TiCjl! a 100
The reaction conditions were maintained for 90 minutes instead of 3 hours, and then the following procedures and ingredients were used before washing.

1.0 g (4.3 mmol) of ZrC1a.
A slurry in 100 ml of 2-dichloroethane was added to the resulting solid and the reaction mixture was heated to 60° C. under nitrogen with stirring at 25 Orpm for 30 minutes. Reaction conditions were maintained for 90 minutes. Then the stirring was stopped and the solids
It was allowed to settle for about 20 minutes at 0°C. The supernatant was then removed and the solid was treated again with ZrC1 in exactly the same way. The supernatant was then removed and the resulting solid was washed with 50 portions of 1,2-dichloroethane five times at 60° C., three times at room temperature, and twice with 50 In1 hexane at room temperature. Elemental analysis shows that the catalyst components are 12.3%, 0.6% Ti, and 16.4%.
It was shown that Zr was included.

Example 17 The procedure and ingredients of Example 1 were used, but 4.9 g of preactivated anhydrous MgCl□ support was substituted for 5.1 g, and 3.4 g (11 mmol) HfCj2. Zr
Used in place of ClaO, 100ml (0.90mol) Tr
50m across Cla! , the separated first solid was not washed before the second treatment, and after the second treatment but before drying the solid, hexane was used 5 times at 60"C and 5 times at room temperature (3 times at each temperature). elemental analysis showed that the catalyst components were 9.4% Mg, 2.2% Ti and 2
It had 6.8% Hf.

Example 1 The procedure and ingredients of Example 1 were used, but 1.2 g
(5.1 mmol) ZrCff4 was used in place of 2.5 g, the first solid was not washed, and the next procedure and ingredients were used.

1.7 g (5.3 mmol) HfCj2. 1, 2
A slurry in 50 ml of -dichloroethane was added to the resulting solid and the reaction mixture was heated to 60°C under nitrogen with stirring at 25 Orpm for 30 minutes. The reaction conditions were set to 90
It was maintained for a minute. Then stop stirring and cool the solid to 60°C.
The mixture was allowed to settle for about 20 minutes. Then, the supernatant liquid was removed, and the resulting solid was heated at 60°C with 1 part of 50ml of 1,2-dichloroethane.
and three times at room temperature, then two times with 50 mf portions of hexane at room temperature.

While slurried in the final wash, the supported catalyst components were transferred into a Shusink flask and dried in the conventional manner. The catalyst components are 11.6% Mg, 1.2% Tl, 8.5% by elemental analysis.
% Zr and 11.2% Hf.

Example 19 The procedure and ingredients of Example 8 were used, but 2.5a
A slurry of (11 mmol) lrcn4 in 100 d of 1,2-dichloroethane was added to 5,2 in the first treatment.
g Zrcf4 and 50 ml knee) T+CR
Used in place of +, partially activated anhydrous', l g Cl3
5.1 g of carrier was used instead of 5.6 g, and the reaction mixture was
Heat to 60°C instead of 100°C for a period of time, hold at that temperature for 90 minutes instead of 3 hours, and solidify at 10°C.
Precipitate at 60°C instead of 0°C, remove the supernatant liquid,
The resulting solid was diluted with 50 ml of 1,2-dichloroethane.
5 times at 60° C. and then twice at 60° C. with 1 part 50 ml hexane, followed by the following operations and using the ingredients.

50d (0.45 mol) neat TiCff to the resulting solid
1° and the reaction mixture was heated to 30°C under a low argon flow.
m (heated with solder to 100°C for 1 hour).

Reaction conditions were maintained for 90 minutes. Stirring was then stopped and the solids were allowed to settle at 100° C. for approximately 20 minutes.

Then, the supernatant liquid was removed, and the resulting solid was dissolved in 50ml of hexane.
One portion was washed 5 times at 60° C. and 5 times at room temperature.

Elemental analysis showed that the catalyst components contained 11.8% Mg, 3.4% Ti and 16.0% Zr.

The catalytic polymerizations of Examples 1-7.15 and I7 were conducted in an Igal stirred batch reactor that was purged with hot argon for 1 hour, cooled, and then purged with gaseous propylene. Using the standard Shusink method, the solid catalyst component was 0. (
11-0.03 g and 6.7 mmol of activator in 5
Premixed in 0-75ml hexane under inert atmosphere for 5 hours and charged into the reactor. When the electron donor was used with the activator, it was premixed with the activator for 5 minutes before mixing with the solid catalyst component. The aluminum to electron donor ratio was varied from 20 to 80:1 when the donor was used. Liquid propylene 2,21 was then charged into the reactor. When used, hydrogen is charged into the reactor in the amount necessary to reduce the molecular weight to the desired range and the reactor is
Heat to ~80°C for 5 minutes. The temperature was maintained for 2 hours.

The reactor was then vented and purged with argon. The polymer was transferred and dried under vacuum at 80°C for 2 hours. When necessary, the polymer was frozen in liquid nitrogen and then ground to an average particle size of approximately IM before analysis. The relevant conditions, components and analysis results are shown in Table 1.

Example 20 Using the catalyst components of Example 2, the polymerization procedure for Examples 1-7.15 and 17 was used, but 33 g (0,
58 mol) 1-butene was added to the reactor after adding liquid propylene but before heating to the reaction temperature used. The resulting copolymers were both measured at 145°C by DSC.
Tm and 15J/g(7)ΔHf, and 2'3C
It had about 2.6% butene from N M RC.

Example 21 Using the catalyst components of Example 2 and using the polymerization procedures for Examples 1 to 7.15 and 17, the polymerization reaction was carried out only after about 100 g of ethylene had been heated to the reaction conditions used for the contents. Added incrementally.

The resulting copolymer had no Tm observed from 40°C to 200°C by DSC and had about 15% ethylene by 1''CNMR.

Example 22 The catalyst component of Example 2 was added to 10 mmol T I B , 4.
), using the polymerization procedure for Examples 1-7.15 and 17, but 2. Ok inbutane was used as a diluent instead of 2,21 liquid propylene, the reaction temperature was maintained for 3 hours instead of 2 hours, ethylene was added starting before heating and then continuously, and the pressure was increased to about 3
00 psi was maintained.

Relevant conditions, components and analytical results for Examples 20-22 Excluding polyethylene: 1) about 50 to about 90
% room temperature xylene soluble fraction, 2) an intrinsic viscosity of about 1.0 to about 6.0 in the absence of chain transfer agent, 3) 1413-160°C as measured by DSC when observed.
Polymerization (wood melting point (Tm)), and crystallinity measured by the heat of fusion (ΔHff), which varies linearly and is typically from about 13 to about 28, as opposed to 4〉% It is a soft or rubbery polymer.

Catalyst yield is approximately 9.0% for 2 to 3 hours of polymerization reaction. (11)
0 to 60,000 g polymer/g catalyst.

Polyethylene made with the catalysts of the present invention may have a 1. V, is shown. Polyethylene made with the catalyst of the present invention: typically wider than polyethylene made with a magnesium chloride-supported titanium tetrachloride solid catalyst component/Ariiso aluminum compound cocatalyst system), a wide molecular pot. Show the distribution.

Polymers and copolymers made with the catalysts of the present invention having an electron donor in the solid catalyst component, ■) a xylene soluble fraction of about 5 to about 60%, 2) a ~10, 3) exhibits a lower heat of fusion compared to high isotactic polymers as measured by DSC, and 4) an XSR greater than or equal to 0.50.
I of the T fraction.

V, and r, v, of the total polymer. DS
The degree of crystallinity from the hotness of melting ΔHf) measured by C is
Isotactic prepared using a solid catalyst component comprising a halogen-containing titanium compound and an electron donor supported on activated magnesium dihalosaponide, especially magnesium dichloride, together with a trialkylaluminium activator and an electron donor as cocatalysts. lower (typically 20-90 J/g) for polymers of the invention made with electron donor-containing solid catalyst components than for polymers or copolymers (typically 100 J/g). ).

-I'G, the polymers and copolymers of the invention are of controlled stereoregularity as evidenced by their xylene soluble fraction at room temperature, with an XSRT fraction greater than or equal to 0.50. The ratio of 1/V, to the total polymer I, V, is shown. Additionally, propylene polymers with high %XSRT typically have 0
．． It exhibits a ratio of XSRT fraction I, V, to total polymer greater than or equal to 70 and has improved elongation at break and elongation set properties compared to commercially available isotactic polymers.

Furthermore, the polymers of the present invention have an I, V of less than 0.5.

is a waxy, solid, low molecular weight polymer with a higher [,V, than commercially available active polymers commonly used as adhesive layers in multilayer structures.

The polymers of the present invention further have an isotacticity of 45 to about 85% and an isotacticity of 140 to 160% as determined by the number fraction of isotactic pentads from CNMR analysis.
It is characterized by its melting point in °C.

The polymers of this invention can be used to make films, -axial and biaxial; fibers; injection and compression molded articles, and extruded articles. They can also be used in fabric and extrusion coating applications and true melt adhesives.

The polymers of the present invention may contain one or more fillers such as alumina trihydrate, talc, calcium carbonate, wollastonite (C
aSiO3), mica, metal flakes, glass flakes,
Glass powder, glass spheres, glass fibers, carbon fibers, metal fibers and aramid fibers can be blended. When fillers are present, they typically account for about 1 to 50% of the polymeric material.
Present in a total amount of 40 weight percent.

Common additives such as stabilizers and pigments can also be present. Antioxidant type stabilizers can be present at about 0.05 to 1.0 pph (parts per hundred) based on the weight of the polymeric material. Acid neutralizers, if used, are typically present in an amount of about 0.05 to 5 pph, preferably about 0.05 to 0.2 pph, based on the weight of the polymeric material. The heat stabilizer is about 0.05 to 1 ppm based on the weight of the polymeric material.
It can be used in the amount of h. The pigment can be used in an amount of about 0.2 to 5, preferably about 2 to 3 pph, based on the weight of the polymeric material.

Typical antioxidants include hindered phenolic compounds such as tetrakis[methylene(3,5-ditertiary-butyl-4-hydroxyhydrocinnamate))methane. Suitable acid neutralizing agents include alkali and alkaline earth metal stearates such as sodium stearate and calcium stearate. 1,000 onysters (e.g. trilauryltrithiophospha) (TLT
TP) and distearylthiodiprobionate (DS
TDP) is a typical heat stabilizer. Suitable pigments include carbon black and titanium dioxide.

Other features, advantages and aspects of the invention disclosed herein include:
It will be readily apparent to those skilled in the art after reading the above disclosure. In this regard, although certain embodiments of the invention have been described in considerable detail, changes and modifications to these embodiments can be made without departing from the spirit and scope of the invention as described and claimed.

Claims (20)

[Claims] (1) One is a halogen-containing titanium metal compound, and one
comprising an activated anhydrous MgCl_2 or its alcohol adduct solid support treated with at least one treatment of at least two halogen-containing transition metal compounds, wherein the compound is a halogen-containing non-titanium transition metal compound, optionally in the presence of an electron donor; Solid catalyst component. (2) Halogen-containing transition metal compound is Sc, Ti, Zr
, Hf, V, Nb, and Ta halides, oxyhalides, C_1-_1_2 alkoxy halides, hydride halides, and C_1-_1_2 alkyl halides, the solid catalyst component according to claim (1). (3) The solid catalyst component according to claim (1), wherein the halogen-containing transition metal compound is selected from the group consisting of chlorides of Ti, Zr, and Hf. (4) Transition metal compound is 5 to 1 per mole of MgCl_2
A solid catalyst component according to claim 1, which is present in an amount of 00 mol. (5) Anhydrous activated MgCl_2, its alcohol adduct or its non-activated precursor is combined in an inert atmosphere with at least two halogen-containing titanium compounds and one halogen-containing non-titanium transition metal compound. At least one treatment, sequentially or simultaneously or both, of halogen-containing transition metal compounds, optionally in the presence of a polar liquid medium and an electron donor, initially at 0°C and then at 30-12°C.
A method for preparing a solid catalyst component comprising treating at a temperature of 0<0>C for 30 to 240 minutes for each treatment, with solids being separated in the middle of the treatment. (6) The method of claim (5), wherein the activated anhydrous MgCl_2 is first treated with a halogen-containing titanium compound and then with a halogen-containing non-titanium transition metal compound. (7) The metal of the halogen-containing non-titanium transition metal compound is S
7. The method according to claim 6, wherein the metal is selected from the group consisting of c, Zr, Hf, V, Nb and Ta. (8) activated anhydrous MgCl_2 is treated with a halogen-containing titanium compound and at least one halogen-containing non-titanium transition metal compound, then with a halogen-containing titanium compound alone or in combination with the same or different halogen-containing non-titanium transition metal compound; The method according to claim (5). (9) activated anhydrous MgCl_2 with a halogen-containing titanium compound and optionally at least one halogen-containing non-titanium transition metal compound, then at least one halogen-containing non-titanium transition metal compound alone or with a halogen-containing titanium transition metal compound; 6. The method of claim 5, wherein the combination is then treated with the same or different halogen-containing non-titanium transition metal compound used in the immediately preceding treatment. (10) A catalyst for the polymerization of at least one α-olefin, the catalyst comprising: (a) an organometallic compound as an activator;
optionally together with an electron donor, and (b) claim (
1) A catalyst comprising the solid catalyst component described above. (11) A catalyst for the polymerization of at least one α-olefin, comprising: (a) an organometallic compound as an activator;
optionally together with an electron donor, and (b) claim (
2) A catalyst comprising the solid catalyst component described above. (12) A catalyst for the polymerization of at least one α-olefin, comprising: (a) an organometallic compound as an activator;
optionally together with an electron donor, and (b) claim (
3) A catalyst comprising the solid catalyst component described above. (13) A catalyst for the polymerization of at least one α-olefin, comprising: (a) an organometallic compound as an activator;
optionally together with an electron donor, and (b) claim (
4) A catalyst comprising the solid catalyst component described above. (14) Formula CH_2=CHR (in the formula, R is C_1 to_1
At least one α-olefin monomer (which is a branched or straight-chain alkyl or an unsubstituted or substituted cycloalkyl) in an inert hydrocarbon solvent and claim (10)
) at a temperature of from about 50 to about 80°C in the presence of a catalyst described in
A method of polymerizing alpha-olefins comprising polymerizing for ~4 hours and recovering the resulting polymer. Formula (15), CH_2=CHR (in the formula, R is C_1~_
1_2 branched or straight-chain alkyl or unsubstituted or substituted cycloalkyl) in the absence of an electron donor in claim (b)
10) produced by polymerization with the catalyst described in (
i) about 50 to about 90% room temperature xylene soluble fraction; (ii)
) an intrinsic viscosity of about 1.0 to about 6.0 in the absence of a chain transfer agent, (iii) a polymer melting point (Tm) of 140 to 160°C as measured by DSC when observed;
ix) varies linearly inversely to XSRT, from about 13 to about 2
A product comprising a polymer having a degree of crystallinity measured by heat of fusion (ΔHf) of 8. (16) Formula CH_2=CHR (in the formula, R is C_1 to_1
claim (1) in which there is no electron donor present in (b);
1) is produced by polymerization with the catalyst described in (i
) about 50 to about 90% room temperature xylene soluble fraction; (ii)
an intrinsic viscosity of about 1.0 to about 6.0 in the absence of a chain transfer agent, (iii) a polymer melting point (Tm) of 140 to 160°C as measured by DSC when observed, and (i
v) A product comprising a polymer having a degree of crystallinity as measured by the heat of fusion (ΔHf) that varies linearly inversely to the room temperature xylene soluble fraction and is from about 13 to about 28. (17) Formula CH_2=CHR (in the formula, R is C_1 to_1
_2 branched or straight-chain alkyl or unsubstituted or substituted cycloalkyl) in the absence of an electron donor in claim (1)
2) is produced by polymerization with the catalyst described in (i
) about 50 to about 90% room temperature xylene soluble fraction; (ii)
an intrinsic viscosity of about 1.0 to about 6.0 in the absence of a chain transfer agent, (iii) a polymer melting point (Tm) of 140 to 160°C as measured by DSC when observed, and (i
v) varies linearly opposite to XSRT, from about 13 to about 28
A product comprising a polymer having a degree of crystallinity as measured by the heat of fusion (ΔHf). (18) Formula CH_2=CHR (in the formula, R is C_1 to_1
_2-branched or straight-chain alkyl or unsubstituted or substituted cycloalkyl); (i) a xylene soluble fraction of about 5 to about 50%; (ii) ) of about 2 to 10 in the absence of chain transfer agent. V. , (iii) a reduction in the heat of fusion for highly isotactic olefin polymers as measured by DSC, and (iv) an I.V. of the XSRT fraction greater than or equal to 0.50. V. and total polymer I. V
．． an olefinic polymer material comprising a polymer having a ratio of (19) Polymerizing at least one α-olefin of the formula CH_2=CHR (wherein R is H) with the catalyst of claim (10) in which no electron donor is present in (b). Products manufactured by. (20) formula, CH_2=CHR (in the formula, R is H)
A product prepared by polymerizing at least one α-olefin of with a catalyst according to claim 11 in which there is no electron donor present in (b).